Polymerization of olefins with bf3



United States Patent Office 3,382,291 POLYMERIZATION 8F OLEFINS WITH BFJames A. Brennan, Cherry Hill N.J., assignor to Mobil Oil Corporation, acorporation of New York o Drawing. Filed Apr. 23, 1965, Ser. No. 450,536

2 Claims. (Cl. 260-683.l5)

ABSTRACT OF THE DISCLOSURE In polymerizing a l-olefin to an oilypolymer, greater reproducibility is obtained by feeding to a reactionzone a stream (1) of a l-olefin that is saturated with BF and a stream(2) of BF complexed in a 1:1 molar ratio with a. promoter. BF and BFcomplex are the sole catalyst components. The process is particularlyuseful for producing synthetic lubricants.

This invention relates to olefin polymerization. It is more particularlyconcerned with a controllable process for polymerizing l-olefins withboron trifiuoride catalyst.

In United States Letters Patent No. 3,149,178, there are describedpoly-l-olefin synthetic lubricants. Depending upon the method ofpolymerization, thermal or catalytic with dialkyl peroxide or with aFriedel-Crafts catalyst, such as A101 and BF a range of viscosities canbe achieved.

In the particular case of BF it has been found extremely difficult tocontrol the reaction temperature and to avoid local overheating (hotspots). Consequently, reproducibility of the polymerization from run torun is poor. Various means have been proposed to solve the problemsinvolved, but most proposals call for relatively elaborate equipment orinvolved manipulations, or both.

It has now been found. that BF -catalyzed olefin polymerization can becarried out to give good reproducibility by a process that is relativelysimple and economically feasible. It has been discovered that suchresults can be achieved by certain rather simple manipulative steps.

Accordingly, it is a broad object of this invention to provide animproved process for carrying out BF -catalyzed olefin polymerization.Another object is to provide a simple and economically feasible processfor carrying out BF -catalyzed olefin polymerization. A specific objectis to provide relatively simple, reproducible process for effecting BF-catalyzed olefin polymerization. Other objects and advantages of thisinvention will become apparent to those skilled in the art, from thefollowing detailed description.

In general, this invention provides a reproducible process forpolymerizing a l-o-lefin to an oily liquid polymer that comprisesfeeding to a reaction zone a stream (1) of l-olefin saturated with BFand a stream (2) of BF c-omplexed in a 1:1 molar ratio with a promoter,and commingling said streams 1) and (2) in said reaction Zone underpolymerization reaction conditions.

In accordance with Patent No. 3,149,178, the improved syntheticlubricants are produced from l-decene or from mixtures of l-olefinshaving between about 6 and about 12 carbon atoms having a mean value ofthe olefin chain length of about carbon atoms. The process technique ofthis invention, however, is not limited to the preferred 3,382,291Patented May 7, 1968 olefins defined No. 3,149,178, but it is applicableto the polymerization of any polymerizable l-olefin or mixtures thereof.Thus, the l-olefin charge can be any normally liquid l-olefin havingbetween about 5 and about 20 carbon atoms or mixtures of such l-olefins.Non-limiting examples of the l-olefin charg are l-pen-tene; 3-methyl-l-butene; l-hexene; 3,3-dimethyl-1-butene; 2,3-dimethyl-l-butene;l-heptene; l-octene; 2,3,3-trimethyl-1- pentene; 2-ethyl-1-hexene;l-decene; l-undecene; l-dodecene; l-tetradecene; l-hexadecene,l-octadecene, and l-eicosene.

The l-olefin charge, i.e., a l-olefin or mixture of l-olefins, issaturated with BB; at room temperature (about 20 C.), before it ischarged to the reaction zone. This can be accomplished by any means wellknown to those skilled in the art. Thus, the l-olefin charge can besaturated by bubbling B1 gas through a l-olefin batch, as in a storagevessel or it can be saturated by bubbling BF gas through a l-olefincharge stream as it passes en route to the reaction vessel. A convenientmethod for accomplishing the .latter would be to use conventional gasscrubbing equipment for countercurrent contact of a gas with a liquid.

As is well known, BF per se is a poor catalyst for polymerizing olefins,unless it is promoted with water or other substances capable of formingcoordination cOmpounds as noted hereinafter. Therefore, in order toaccomplish the purpose of the process of this invention, the 1-olefinsaturated with BB, should be free of water and other impurities.

The second. stream that is charged to the reactor is a 1:1 molar complexof B1 and a promoter compound. This complex, upon contacting the firststream (l-olefin charge) in the reactor, effects the polymerizationreaction. The promoter compound used to form BF -promoter catalystcomplexes are well known in the art. They include, by way ofnon-limiting examples, water; alcohols, such as octanol and l-decanol;acids, such as acetic acid, propionic acid, and butyric acid; ethers,such as diethyl ether; acid anhydrides such as acetic acid anhydride andsuccinic anhydride; esters, such as ethyl acetate and methylpro'pionate; and ketones and aldehydes, such as acetone andbenzaldehyde.

As will be appreciated. by those skilled in the art, the rate at whichthe streams (1) and (2) are charged to the reactor can vary widely,dependent in part upon the size of the reactor, but primarily upon thecooling capacity of the reactor. Thus, the rate of addition of thestreams is limited only by the ability to remove exothermic heat ofpolymerization, so as to maintain a predetermined polymerizationtemperature.

An important feature of the process of this invention is that the rateof addition of stream (2) (BF -promoter) relative to the rate ofaddition of stream (1) (l-olefin saturated by BF be adjusted to add onlya catalytic amount and to avoid any excess over the catalytic amount.This rate is conveniently expressed in terms of moles of promoter perWeight unit of olefin. This rate will be between about 0.006 molepromoter and about 0.01 mole promoter per g. of l-olefin charge. Usingthis relative rate of addition, a uniform rate of polymerization isattained and local overheating is avoided, thus permittingreproducibility of results from run to run.

The process of this invention is carried out using the usual conditionsfor BF -catalyzed polymerization of 1- olefins. The temperature isgenerally below about 60 C. and preferably between about C. and about 35C. The reaction can be carried out at atmospheric pressure, but moderatepressures of from about one p.s.i.g. up to about 500 p.s.i.g. arepreferred.

In the usual batch operation, after addition of l-olefin charge iscompleted, the reaction mixture is generally held at the reactiontemperature for an additional period of time. This hold time willusually be between about 1 hour and about 3 hours, although higher holdtimes can be used. The process of this invention can also be carried outcontinuously by withdrawing a product stream at This run gave a 98%conversion to polymer and the following oligomer distribution:

Percent Dimer 10.6 Trimer 39.0 Residual 49.5

Examples 2 through 8 Table.1he BFa Polymerization of 1-Deeene.-Efieet ofReact-ion Variables Hold Promoter, 1 Oligomer Distribution, OlefinExample Temp., Pressure, Add. Rate, 'lime, Molos/ G. Olefin Percentpercent of Total Trimer C. in. Hg Percent/Min. lirs. 100 g. OlefinConversion K.V. at 65 F.

Dimer 'Irimer Residual Temperature Promoter Gone.

Add. Rate Pressure Hold Time 1 Promoter is l-decanol.

2 The high viscosity is attributed to contamination. Hydrogenation ofthis olefin resulted in a high quality fluid.

the rate of infiueut streams. After stable state reaction is reached,the average residence time will be equal to the aforedescribed holdtime, thus affording a uniform product.

In the following examples, the techniques of the process of thisinvention are demonstrated, using the polymerization of l-decene with BF-1-decanol as illustrative. It will be understood, however, that themethod so demonstrated can be applied to other l-olefins and promotersdescribed hereinbefore, as those skilled in the art will readi- 1yappreciate.

Example 1 l-decene was pumped through the bottom of a water trap,saturated with BF and allowed to overflow into the reaction flask.l-decanol complexed with BF in a mole ratio of 1 (promoter) was pumpeddirectly into the reaction flask. The rates of these solutions were 23.8ml./hr. and 0.29 ml./hr., respectively. These rates gave a promoterconcentration of 0.008 mole per 100 g. of olefin. The reaction flask waspressured to 4 inches of mercury and maintained at 30 C. by means ofcirculating water. After complete addition of the charge, the reactorwas held for one hour, at the above conditions, depressurized and sweptwith nitrogen. The product was neutralized with gaseous ammonia, heatedat 80 C. for one hour (N filtered, water washed until neutral, dried andfinally distilled at reduced pressure.

The oligomers can be separated at the conditions shown below:

From the examples, it will be apparent that the process of thisinvention produces poly-l-decene in good yield and with desirableoligomer distribution, i.e., with a minimum formation of undesirabledimer (US. 3,149,178). Trimer and higher distribution can be varied bychanging variables, but with each set of conditions results arereproducible. It will be noted that in the case of Example 4, lowconversion only to dimer was achieved. In this run, however, thepromoter concentration was below the range set forth hereinbefore.

It will be appreciated that the technique of this invention can beapplied to other reactions catalyzed with BF Thus, for example,alkylation of an aromatic hydrocarbon with an olefin can be effected bycharging a stream of olefin and aromatic hydrocarbon saturated with BFand a stream of 1:1 molar ratio El -promoter complex, under alkylationreaction conditions.

Although the present invention has been described with preferredembodiments, it is to be understood that modifications and variationsmay be resorted to, without departing from the spirit and scope of thisinvention, as those skilled in the art will readily understand. Suchvariations and modifications are considered to be within the purview andscope of the appended claims.

What is claimed is:

1. A reproducible process for polymerizing a 1-olefin having between 5and 20 carbon atoms to an oily liquid polymer that comprises feeding toa reaction zone a stream (1) of said l-olefin saturated with BF and astream (2) of B1 oomplexed, in a 1:1 molar ratio, with a promoter,commingling said streams (1) and (2) in said reaction zone underpolymerization reaction conditions, and controlling the relative rate ofaddition of streams (1) and (2) to charge between about 0.006 mole andabout 0.01 mole promoter per 100 g. of l-olefin;

said BF and said BF complexed with a promoter being the sole catalystsystem.

2. A reproducible process for polymerizing l-decene to an oily liquidpoly-l-decene that comprises feeding to a reaction zone a stream (1) ofsaid l-decene saturated with BF and a stream (2) of BF complexed, in a1:1 molar ratio, with l-decanol, commingling said streams (1) and (2) insaid reaction zone under polymerization reactions, and controlling therelative rate of addition of said streams (1) and (2) to charge betweenabout 0.006 mole and about 0.01 mole l-decanol per 100 g. of l-decene.

References Cited UNITED STATES PATENTS 2,603,666 7/1952 Fritz 260683.152,766,312 10/1956 Serniuk 260-68315 3,149,178 9/1964 Hamilton et al260--683.9

PAUL M. COUGHLAN, 111., Primary Examiner.

UNITED STAT-ES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,382,291 May 7, 1968 James A. Brennan It is certified that errorappears in the above identified patent and that said Letters Patent arehereby corrected as shown below:'

Columns 3 and 4, in the Table, sixth column, line 7 thereof; "1 .016"should read 0 .016 Same sixth column, line 9 thereof, "1.008" shouldread 0.008 Column 5, lines 8 and 9, "reactions" should read conditionsSigned and sealed this 7th day of October 1969.

(SEAL) Attest:

Edward M. Fletcher, Jr. E.

Attesting Officer Commissioner of Patents

